Lina: Would always win because she would Dragon Slave the studio if she didn't. She would also get the best prizes and the most money of all of the contestants.
Gourry: Wouldn't know how to spell any of the words, including the simple ones, and therefore wouldn't do too terribly well.
Amelia: Would try to win in the name of justice. Would also give justice speeches every time she had to choose a letter, therefor turning a half hour gameshow into an hour long test of patience.
Sylphiel: Would use her divine powers to not go bankrupt or lose a turn, but would still have problems with the spelling.
Zelgadis: Would summon the spirits of the elements to give him the maximum cash for every time he spun the wheel. He also has a large intellect so he would win, hands down, with a minimum of effort.
Xellos: Would become a woman to sleep with the host. Would then become a handsome and charming man to sleep with Vanna White. The first two things would be for the hell of it since he would simply use his Mazoku powers to make the wheel do his bidding. However he would simply reply, "Sore Wa, Himitsu Desu" whenever asked for a letter.
Filia: Would invoke the powers of the Fire Dragon King for knowledge, luck, and sex appeal. Would also turn into a dragon if she lost any of the rounds and probably trash the studio with just the transformation, let alone anything else.
Martina: Would threaten the host and the other players with the wrath of Zoamelgustar if she isn't proclaimed the winner after the opening puzzle. If all else fails she could simply cry and plot the demise of the host or the other players and use her obsession to cast a powerful curse.
Phibrizo: Would threaten to crush the soul sphere of Vanna if he isn't allowed to spin, spin, SPIN for the most money, not lose any to bankruptcy, not lose any turns for wrong letter guesses, and then given the best, if not all of the prizes for the daily champion.
Garv: Wouldn't do too much except curse enough to cause the studio executives to give him whatever he wants just to make him stop cursing and swearing.
Rezo: Would summon the power of Shabrinigdo to be his eyes so that he could actually see the puzzle. We all know what happened after that...
Copy Rezo: Would summon the demon beast Zannifar and try to outdo the original Rezo in solving puzzles, guessing letters, spinning the wheel, and otherwise driving everyone insane with the two large snarling dragon heads that appeared when summoning Zannifar.
Valgarv: Now why would he waste his precious time on a game show when there is a world to be conquored and destroyed.